Naphthophenazine dyestuffs



Patented 0st. 2, i928.

UNITE srars* WILHELM NEELMEIER, 0F LEVERKUSEN, NEAR, COLOGNE-ON-TI-IE-RHINE, AND THEO- DOB NOGKEN, OF WIESDOR-F, NEAR COLOGNE-ON-TI-IE-RHINE, GERMANY, AS-

SIGNORS TO GRASSELLI DYESTUFF CORPORATIQN, OF NEW YORK, N. Y., A COR-PO- RATION OF DELAWARE.

N API-ITHOPHENAZIN E DYESTUIEFS.

No Drawing. Application filed June 9, 1926, Serial No. 114,803, and in Germany June 12, 1925.

Our invention consists in novel naphthophenazine dyestuffs from 1-3-di(p-alkoxyarylamino) naphthalenes.

In the German Patents 78,497, 79,189, 80,778, 86,222, 88,228, 88,22 l,206,64-6 and the United States Letters Patent 8025a, 603,013, 606,295 and 94035 1 azine dyestuifs and processes of making the same are described which are obtained from 1-3-diaryl-naphthylene diamine sulfonic acids and for which the generally admitted chemical constitution can be represented by the schematic graphical formula A 1y \NHZ Aryl I Aryl The most important reactions leading to these naphthophenazine dyestuffs are condensation of the 1-3-diaryl-naphthylene-diamine compounds with p-nitroso-amino-aryl compounds or condensation of the same na-phthylene diamines wit-h p-amino-azo compounds or joint oxydation of the naphthylene-diamines with para-diamines.

The fast-ness to light of these dyestufis is now considerably improved, while the other fastness properties remain practically the same if instead of the di-phenyl or di-tolyl-l- S-naphthylene diamines described so far for these reactions para-alkyloXy-aryl-amino substituted 1-3-naphthylene-diamine compounds are used to produce the naphthophenazine dyestuffs.

The chemical constitution of our novel phenazine dyestuffs obtained in this manner 1s probably quite similar and can be represented by the schematic formula Alkyl 0-Alky1 tached to the benzene nucleus in the naphthophenazine ring can be replaced by alkyl or aryl radicles and the naphthalene, as well as the benzene rings of the naphthophenazine nucleus can be substituted by sulfo groups, the naphthalene ring preferably in 8 posit-ion, or other common substituents.

Our novel dyestuffs are generally dark powders with metallic lustre, they are soluble in water with blue to violet colors, soluble in concentrated sulfuric acid with green colors and dye wool from acid baths very level greenish-blue to violet shades of particularly good fastncss to light. y

The 1 3-di p-alkoxyarylamino) naphthalene compounds are easily prepared from 1-naphthylamine-3-sulfonic acid compounds by reacting upon same with 1-amino-4alkoXybenzene compounds.

Our invention is further illustrated by the following examples, the parts being by weight, but it is understood, that our invention is not limited to the specific dyestuffs described.

Ezra-mph 1. l50 parts 1-3-di(l-methoxyphenylamino)naphthalene 8 sulfonic acid are dissolved in 6000 parts 50% alcohol and neutralized with soda ash; tothisasolution of 216 parts Lamino-dimethylaniline3-sulfonic acid in 2000 parts 50% alcohol, 53 parts soda ash and 50 parts of a cuprammonium solution corresponding to 20 parts blue vitrol are added; the reaction mass is then heated to 5060 C. and with stirring a current of air blown through. The dyest-uff is completely formed and precipitated after several hours blowing. It is filtered oii' and if need be recrystallized from hot water. After drying it is obtained as a dark powder having a cuprous lustre, it is soluble in water with a blue and in concentrated sulfuric acid with a green color, it dyes wool level. greenish-blue shades, particularly fast to light.

The dyestufl can be represented by the most probable formula A/My N(CHa)z Example .@.530 parts'l-S-di (dancthoxyphenylamino)naphthalene 6 8 disulfonic acid are stirred up in 10,000 parts alcohol with 225 parts para-nitroso-dirnethylaniline and heated to boiling temperature; the reaction proceeds quickly-with the formation of the azine dyestutl. After cooling it is filtered off and is isolated in the usual manner. It is a dark powder having a cuprous lustre, it is soluble in water with a blue color and in conccntrated sulfuric acid with a green color and dyes wool level, clear blue shades of good fastness to light. The dyestulf can be represented by the most probable graphical formula soin 0H3 (iom Emcmzple 3.The dyestu'tl of the probable formula which can be obtained by joint oxidation of 1-3 di (4 ethoxyphenylamino) naph thal ene- S-sulfonic acid and l-amino-dimethylaniline- 3-sulfonic acid is 2 dark powder with a cuprous lustre, soluble in water with a blue, in concentrated sulfuric acid with a green color and dyes wool level, very greenish-blue shades of excellent fastness to light.

Eavmiple /,1.-By joint oxidation of Lil-di- (4-methoXyphenylamino) naphthaletre-S-sut fonic acid with p-phenyletnediamine-sulphonic acid a dyestufl' is obtained which can be rep resented by the mos probable formula It a brown powder with a metallic lustre, soluble in water with a violet color, soluble in concentrated sulfuric acid with a green color and dyes wool level, bluish-violet shades of good milling and excellent light fastnesa \Ve claim I 1. As new products naphthophenazine dyestuffs of the general type in which R stands for hydrogen, an alkyl or an. aryl radicle, and in which the naphthophenazine nucleus may contain additional sult'o groups, which are dark powders with metallic lustre, soluble in water With from violet to blue colors, soluble in concentrated sulfuric acid with a green color, dyeing wool from violet to blue shades, particularly fast to light and which are substantially identical with the products obtainable by submitting 1 3 di (para-allioxyarylamino) naphthalene compounds and para-diamino-aryl compounds to reactions leading to the formation of the 'n mphthophenazine nucleus.

2. As new products naphthophenazine dyestuffs of the general type nois Alkyl lIEO 3. As a new product the naphthophenazine dyestufl' having most probably the formula 1 CH3 0 CH3 which is a brown powder With metallic lustre,

soluble in water with e violet eoloi', soluble in concentrated sulfuric acid with a green color, dyeing Wool bluish-violet, level shades of excellent fest-ness to light and Whicl is substantially identical with the product obtainable by joint oxidation of l-ll-di- (inethoxyphenylamino)naphthalene 8 sultonic acid and paia-phenylene-diainine sulfonic acid.

In testimony whereof We have hereunto set our hand s.

V ILHELM NEELMEIER. THEODOR NOGKEN. 

